The present invention relates to a novel polymeric compound, a polyurethane containing a metal phthalocyanine in the main chain. The polymer is useful as a material having an ability of photoelectric conversion, a physiological function and a function as a redox catalyst.
Up to now, the metal phthalocyanine has widely been employed as blue and green pigments and dyes. The metal phthalocyanine is a metal complex which has a very stable large cyclic planar ligand and has a tetraazaporphyrin skeleton. Since the metal phthalocyanine forms a special electronic environment having a large .pi. electron system, it has recently attracted special interest as a variety of functional materials such as catalystic, electronic, light-energy conversible and physiological functions although the metal content thereof is very low.
The combination of phthalocyanine having such useful functions to a polymer makes it possible to impart such various functions of phthalocyanine to the resulting polymer. For instance, it becomes possible to design various materials having a variety of functions such as deodorizing polymers and conductive polymers. One example of such techniques is disclosed in Japanese Patent Provisional Publication No. 63-273638 which relates to a polyester containing metal phthalocyanine rings in its main chain.
The inventors of this invention have conducted studies of models of a series of redox enzymes in vivo utilizing metal phthalocyanines having functions similar to those of the metal porphyrin existing in living bodies in order to develop an artificial enzyme. As a result, the inventors have found out that the metal phthalocyanine is preferably combined with a polymeric compound in order to enhance the catalytic function of the metal phthalocyanine as a redox enzyme and thus have completed the present invention.
Accordingly, a first object of the present invention is to provide a polyurethane containing a metal phthalocyanine in the main chain. The polyurethane containing a metal phthalocyanine in the main chain is a novel polymeric compound and shows an excellent catalytic function as a redox enzyme. It is possible to form a variety of molded products from the polymeric compound, such as a film and a block.
A second object of the present invention is to provide a method for preparing a polyurethane containing a metal phthalocyanine in the main chain in high yield.
A third object of the present invention is to provide a redox catalyst comprising a polyurethane containing a metal phthalocyanine in the main chain.
A fourth object of the present invention is to provide a fiber comprising a polyurethane containing a metal phthalocyanine in the main chain. The resulting fiber has a function catalytically promoting the oxidation of mercaptans which are substances giving out bad smell and, therefore, it is useful as a deodorizing fiber.
Fifth object of the present invention is to provide a method for preparing a fiber which comprises a polyurethane containing a metal phthalocyanine in the main chain.
According to an aspect of the present invention, there are two types of polymer structures of polyurethanes containing a metal phthalocyanine in the main chain. One of the polymer structures comprises repeating units represented by the following general formula [I]: ##STR1## wherein R.sup.1 represents a group --(CH.sub.2 CH.sub.2 O).sub.n --C.sub.2 H.sub.4 --(n is an integer of 0 to 3), ##STR2## R.sup.2 represents a group --(CH.sub.2).sub.6 --, --(CH.sub.2).sub.10 -- or --(CH.sub.2 CH.sub.2 O).sub.2 --C.sub.2 H.sub.4 --; M represents a metal atom selected from the group consisting of Co, Fe, Mn, Ti, V, Ni, Cu, Zn, Mo, W, Os and Ca; and x/y ranges from 0.1/99.9 to 90.0/10.0. The polymer has a molecular weight ranging from 1,000 to 200,000.
The other of the polymer structures comprises repeating units represented by the following general formula [II]: ##STR3## wherein R.sup.1, R.sup.2, M and x/y are the same as those defined above in connection with the general formula [I] and which has a molecular weight ranging from 1,000 to 200,000.
According to another aspect of the present invention, there is provided a method for preparing a polyurethane containing a metal phthalocyanine in the main chain represented by the foregoing general formula [I] or [II] which comprises the steps of reacting a metal phthalocyanine polycarboxylic acid with thionyl chloride to obtain a metal phthalocyanine polycarboxylic acid polychloride; synthesizing a metal phthalocyanine polyhydroxy ester from the metal phthalocyanine polycarboxylic acid polychloride and a diol, i.e. HO--R.sup.1 --OH (R.sup.1 is the same as that defined above) through a dehydrochlorination; and then addition-condensation-polymerizing the resulting metal phthalocyanine polyhydroxy ester, a diol, i.e. HO--R.sup.2 --OH (R.sup.2 is the same as that defined above) and a diisocyanate.
According to a further aspect of the present invention, there is provided a polymeric catalyst for redox reactions which comprises a polymer containing a metal phthalocyanine in the main chain composed of repeating units represented by the foregoing general formula [I] or [II].
According to a still another aspect of the present invention, there is provided a fiber which comprises a polyurethane containing a metal phthalocyanine in the main chain composed of repeating units represented by the foregoing general formula [I] or [II].
According to a still further aspect of the present invention, there is provided a method for preparing a fiber which comprises a polyurethane containing a metal phthalocyanine in the main chain composed of repeating units represented by the foregoing general formula [I] or [II], the method comprising the steps of reacting a metal phthalocyanine polycarboxylic acid with thionyl chloride to obtain a metal phthalocyanine polycarboxylic acid polychloride; synthesizing a metal phthalocyanine polyhydroxy ester from the metal phthalocyanine polycarboxylic acid polychloride and a diol, i.e. HO--R.sup.1 --OH (R.sup.1 is the same as that defined above) through a dehydrochlorination; then addition-condensation-polymerizing the resulting metal phthalocyanine polyhydroxy ester, a diol, i.e. HO--R.sup.2 --OH (R.sup.2 is the same as that defined above) and a diisocyanate to obtain a polyurethane containing a metal phthalocyanine in the main chain; dissolving the polyurethane containing a metal phthalocyanine in the main chain in an organic solvent to form a stock solution for spinning, and subjecting the stock solution to wet spinning to form a fiber.